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| United States Patent |
5,047,577
|
|
Smith
, et al.
|
September 10, 1991
|
Quaternary ammonium compounds
Abstract
Peroxygen laundry bleach (e.g. sodium perborate) is activated to be
effective at a lower temperature by use in combination with a
hydrocarbonyloxyhydrocarbyl trihydracarbyl quaternary ammonium salt, e.g.
dodecyldimethyl 2-acetyloxyethylammonium bromide.
| Inventors:
|
Smith; Kim R. (Baton Rouge, LA);
Sauer; Joe D. (Baton Rouge, LA);
Borland; James E. (Baton Rouge, LA)
|
| Assignee:
|
Ethyl Corporation (Richmond, VA)
|
| Appl. No.:
|
894938 |
| Filed:
|
August 8, 1986 |
| Current U.S. Class: |
560/253; 252/186.1; 560/250 |
| Intern'l Class: |
C07C 067/02 |
| Field of Search: |
560/250,253
252/186.1
|
References Cited
U.S. Patent Documents
| 2295504 | Sep., 1942 | Shelton | 560/250.
|
| 2380877 | Jul., 1945 | Shelton | 560/250.
|
| 2541248 | Feb., 1951 | Hibbs.
| |
| 3557214 | Jan., 1971 | Koenig et al. | 560/250.
|
| 4313889 | Feb., 1982 | Bodor | 560/250.
|
| 4470918 | Sep., 1984 | Mosier | 560/155.
|
Primary Examiner: Shaver; Paul F.
Attorney, Agent or Firm: Odenweller; Joseph D., Sieberth; John F.
Parent Case Text
This application is a continuation-in-part of Application Ser. No. 782,353,
filed Oct. 1, 1985, now U.S. Pat. No. 4,883,917.
Claims
We claim:
1. A quaternary ammonium laundry bleach activator having the formula
##STR4##
wherein R.sub.1 and R.sub.2 are alkyls containing 8-20 carbon atoms,
R.sub.3 is methyl, R.sub.4 is --(CH.sub.2 CH.sub.2)--, R.sub.5 is an alkyl
containing 1-20 carbon atoms and X is a monovalent anion.
2. A bleach activator of claim 1 wherein X is halogen.
3. A bleach activator of claim 2 wherein R.sub.5 is an alkyl containing
1-11 carbon atoms.
4. A bleach activator of claim 3 namely, didodecyl-methyl
2-acetyloxyethylammonium chloride.
5. A bleach activator of claim 3 namely, didecylmethyl
2-acetyloxyethylammonium chloride.
6. A bleach activator of claim 3 namely, dioctylmethyl
2-acetyloxyethylammonium chloride.
7. An oxygen bleaching composition comprising a peroxygen bleaching
compound and a bleach activator having the formula
##STR5##
wherein R.sub.1, R.sub.2 and R.sub.3 are aliphatic hydrocarbon groups
containing 1-30 carbon atoms, R.sub.4 is a divalent aliphatic hydrocarbon
group containing 1-12 carbon atoms and R.sub.5 is a hydrocarbon group
containing 1-20 carbon atoms and X is a monovalent anion.
8. A bleaching composition of claim 7 wherein said inorganic peroxygen
bleaching compound is selected from the group consisting of sodium
perborate, sodium perborate hydrates, sodium carbonate peroxyhydrate,
sodium pyrophosphate peroxygen hydrate, urea peroxyhydrate, sodium
peroxide and mixtures thereof.
9. A bleaching composition of claim 7 wherein R.sub.1 is an alkyl
containing 8-20 carbon atoms, R.sub.2 is an alkyl containing 8-20 carbon
atoms or is a methyl group, R.sub.3 is methyl, R.sub.4 is --CH.sub.2
CH.sub.2 --, R.sub.5 is an alkyl containing 1-20 carbon atoms and X is
halogen.
10. A bleaching composition of claim 9 wherein R.sub.1 is an alkyl
containing from 8 to 20 carbon atoms, R.sub.2 and R.sub.3 are methyl,
R.sub.4 is --CH.sub.2 CH.sub.2 -- and R.sub.5 is an alkyl containing 1-11
carbon atoms.
11. A bleaching composition of claim 10 wherein said bleach activator is
hexadecyldimethyl 2-acetyloxyethylammonium chloride.
12. A bleaching composition of claim 10 wherein said bleach activator is
tetradecyldimethyl 2-acetyloxyethylammonium chloride.
13. A bleaching composition of claim 10 wherein said bleach activator is
dodecyldimethyl 2-acetyloxyethylammonium chloride.
14. A bleaching composition of claim 10 wherein said bleach activator is
decyldimethyl 2-acetyloxyethylammonium chloride.
15. A bleaching composition of claim 10 wherein said bleach activator is
dioctyldimethyl 2-acetyloxyethylammonium chloride.
16. A bleaching composition of claim 7 wherein R.sub.1 and R.sub.2 are
alkyls containing 8-20 carbon atoms, R.sub.3 is methyl, R.sub.4 is
--CH.sub.2 CH.sub.2 -- and R.sub.5 is an alkyl containing 1-11 carbon
atoms.
17. A bleaching composition of claim 16 wherein said bleach activator is
didodecylmethyl 2-acetyloxyethylammonium chloride.
18. A bleaching composition of claim 16 wherein said bleach activator is
didecylmethyl 2-acetyloxyethylammonium chloride.
19. A bleaching composition of claim 16 wherein said bleach activator is
dioctylmethyl 2-acetyloxyethylammonium chloride.
20. A bleaching composition of claim 10 wherein said inorganic peroxygen
compound is sodium perborate, a sodium perborate hydrate or mixtures
thereof.
21. A bleaching composition of claim 16 wherein said inorganic peroxygen
compound is sodium perborate, a sodium perborate hydrate or mixtures
thereof.
Description
BACKGROUND OF THE INVENTION
Bleach is commonly used to whiten soiled fabrics during laundry operations.
The most common bleach is aqueous sodium hypochlorite referred to as
chlorine bleach. Chlorine bleach is effective and cheap but has certain
disadvantages. It cannot be mixed with the detergent in a single package.
It tends to attack certain dyes and also degrades fabrics. In addition,
fabrics having a resin finish (wash and wear fabrics) are given a
noticeable yellow tint by chlorine bleach.
In order to overcome these disadvantages, another class of laundry bleach
has come into use. This class is referred to as peroxygen bleach. These
materials are very effective whitening agents and are much safer with dyed
fabrics. In addition they do not yellow wash and wear fabrics. Many can be
packaged together with a detergent and other components to form a single
detergent-bleach laundry package.
Although peroxygen bleaches have these many attributes, they have several
drawbacks. They are more expensive compared to chlorine bleach and also
are not effective unless the wash solution is at a temperature high enough
to activate the peroxygen compound. For example, sodium perborate requires
a water temperature above about 160.F which is higher than that usually
attained in domestic laundry operations. In order to lower the temperature
at which peroxygen bleach can be used, resort is had to "bleach
activators". These are compounds that by themselves have no bleaching
action but when used in combination with a peroxygen bleach form a
peroxygen compound which is effective at lower temperatures than the
initial peroxygen bleach. Examples of such bleach activators are
tetraacetylethylenediamine, sodium p-acetoxybenzene sulfonate and sodium
p-heptanoyloxybenzene sulfonate.
SUMMARY OF THE INVENTION
It has now been discovered that certain
trihydrocarbylhydrocarbonyloxyhydrocarbyl ammonium quaternary ammonium
salts are effective activators for peroxygen bleaching compounds capable
of forming hydrogen peroxide in aqueous solutions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of the invention is an oxygen bleaching composition
comprising a peroxygen bleaching compound and a bleach activator having
the formula
##STR1##
wherein R.sub.1, R.sub.2 and R.sub.3 are aliphatic hydrocarbon groups
containing 1-30 carbon atoms, R.sub.4 is a divalent aliphatic hydrocarbon
group containing 1-12 carbon atoms and R.sub.5 is a hydrocarbon group
containing 1-20 carbon atoms and X is a monovalent anion.
Some examples of the novel bleach activators are
dodecyldimethyl 2-octadeconyloxyethylammonium bromide;
triacontyldecylmethyl 3-eicosonyloxypropylammonium chloride;
tetracontyldodecylethyl 2-hexadeconyloxybutylammonium iodide;
hexadecyldiethyl 8-dodeconyloxyoctylammonium fluoride;
dihexadecylmethyl 10-nonanoyloxydodecylammonium chloride;
dodecyldimethyl 2-benzoyloxyethylammonium bromide;
dioctylethyl 2-phenylacetyloxypropylammonium chloride; and the like.
Another preferred embodiment consists of bleach activators of the above
formula wherein R.sub.1 is an alkyl containing 8-20 carbon atoms, R.sub.2
is an alkyl containing 8-20 carbon atoms or is a methyl group, R.sub.3 is
methyl, R.sub.4 is the group --(CH.sub.2).sub.m -- wherein m is an integer
from 1 to 6, R.sub.5 is an alkyl containing 1-6 carbon atoms and X is a
monovalent anion. Some examples of these activators are:
octyldimethyl 2-acetyloxyethylammonium chloride;
octadecyldimethyl 3-propionyloxypropylammonium iodide;
dioctylmethyl 3-acetyloxyhexylammonium bromide;
didecylmethyl 2-acetyloxyethylammonium bromide;
decyldimethyl 2-acetyloxyethylammonium chloride;
octyldimethyl 2-acetyloxyethylammonium chloride;
dioctylmethyl 2-acetyloxyethylammonium bromide;
dodecyldimethyl 2-acetyloxyethylammonium bromide;
tetradecyldimethyl 2-acetyloxyethylammonium bromide;
octadecyldimethyl 2-acetyloxyethylammonium chloride; and the like.
A highly preferred embodiment of the invention is a bleach activator
wherein R.sub.1 is an alkyl containing 8-20 carbon atoms, R.sub.2 is an
alkyl containing 8-20 carbon atoms or is a methyl group, R.sub.3 is
methyl, R.sub.4 is --CH.sub.2 CH.sub.2 --, R.sub.5 is an alkyl containing
1-20 carbon atoms and X is halogen. Some examples of this embodiment are:
dioctylmethyl 2-acetyloxyethylammonium chloride;
decyloctylmethyl 2-propionyloxyethylammonium bromide;
dodecyleicosylmethyl 2-eicosonyloxyethylammonium iodide;
octadecyldimethyl 2-octadeconyloxyethylammonium chloride;
eicosonyldimethyl 2-acetyloxyethylammonium bromide;
hexadecyloctylmethyl 2-octanoyloxyethylammonium chloride; and the like.
In a still more preferred embodiment, R.sub.1 is an alkyl containing from 8
to 20 carbon atoms, R.sub.2 and R.sub.3 are methyl, R.sub.4 is --CH.sub.2
CH.sub.2 -- and R.sub.5 is an alkyl containing 1-11 carbon atoms.
Examples of these are:
tetradecyldimethyl 2-acetyloxyethylammonium chloride;
dodecyldimethyl 2-acetyloxyethylammonium chloride;
decyldimethyl 2-acetyloxyethylammonium chloride;
octyldimethyl 2-acetyloxyethylammonium chloride;
eicosyldimethyl 2-dodeconyloxyethylammonium chloride;
octadecyldimethyl 2-nonanoyloxyethylammonium bromide;
hexadecyldimethyl 2-octanoyloxyethylammonium chloride;
dodecyldimethyl 2-decanoyloxyethylammonium iodide; and the like.
Another more preferred embodiment of the invention comprises bleach
activators of the above formula in which R.sub.1 and R.sub.2 are alkyls
containing 8-20 carbon atoms, R.sub.3 is methyl, R.sub.4 is --CH.sub.2
CH.sub.2 -- and R.sub.5 is an alkyl containing 1-11 carbon
Examples of these compounds are:
didodecylmethyl 2-acetyloxyethylammonium chloride;
didecylmethyl 2-acetyloxyethylammonium chloride;
dioctylmethyl 2-acetyloxyethylammonium chloride;
dieicosylmethyl 2-dodecanoyloxyethylammonium chloride;
dioctadecylmethyl 2-decanoyloxyethylammonium bromide;
dodecylhexadecylmethyl 2-nonanoyloxyethylammonium iodide;
didodecylmethyl 2-pentanolyoxyethylammonium chloride;
dioctylmethyl 2-butanoyloxyethylammonium bromide; and the like.
The quaternary bleach activators can be made by reacting halohydrocarbyl
esters of carboxylic acids with trihydrocarbyl amines under conventional
quaternary ammonium salt forming reaction conditions. This is shown by the
following equation:
##STR2##
The preparation is shown in the following examples.
EXAMPLE 1
In a reaction vessel was placed 42.8 grams of 2-bromoethyl acetate, 58.9
grams of tetradecyldimethylamine and 107.6 grams of methylethyl ketone
(MEK) solvent. The mixtures was refluxed (ca. 90.degree. C.) under
nitrogen with stirring for 7 hours. The reaction mixture was cooled and
the solvent decanted leaving as the product tetradecyldimethyl
2-acetyloxyethylammonium bromide.
EXAMPLE 2
In a glass reaction vessel was placed 56.3 grams of didecylmethylamine,
32.3 grams of 2-bromoethyl acetate and 102 grams of MEK. The mixture was
stirred under nitrogen at reflux (ca. 86.degree. C.) for 6 hours. It was
then cooled and allowed to stand overnight. In the morning, a crystalline
precipitate had formed which was recovered by filtration. The precipitate
was didecylmethyl 2-acetyloxyethylammonium bromide.
EXAMPLE 3
In a glass reaction vessel under nitrogen was placed 78.25 grams of ethyl
acetate solvent and 32.65 grams of 2-bromoethyl acetate. While stirring,
41.14 grams of dodecyl dimethyl amine was added dropwise. A slight
exotherm was observed. Heat was applied and the temperature raised to
reflux (ca. 89.degree. C.) which was continued for 6 hours. The mixture
was then cooled to -10.degree. C. causing the product to precipitate. The
product, dodecyldimethyl 2-acetyloxyethylammonium bromide, was recovered
by filtration.
The novel bleach activators can also be made by first making a
trihydrocarbyl hydroxyalkyl ammonium halide and then esterifying this by
reaction with a carboxylic acid anhydride or acid halide. This is shown in
the following two equations.
##STR3##
This synthetic method is shown in the following example.
EXAMPLE 4
In a reaction vessel was placed 13.14 grams of dodecyldimethyl
2-hydroxyethylammonium bromide, 21.22 grams of acetone solvent and 4.72
grams of sodium carbonate. While stirring under nitrogen, 3.27 grams of
acetyl chloride was added dropwise. Gas evolution occurred. The mixture
was then refluxed (ca. 60.degree. C.) for 6 hours. The solvent was removed
under vacuum. The residue was extracted with isopropanol to dissolve the
quat and the solution was filtered hot to remove sodium chloride and
sodium carbonate. The filtrate was evaporated under vacuum leaving as the
product dodecyldimethyl 2-acetyloxyethylammonium bromide.
The bleach activators are used in combination with peroxygen bleaching
compounds. These are compounds which are capable of forming hydrogen
peroxide in aqueous solutions. Some examples of these are:
sodium perborate;
sodium perborate monohydrate;
sodium perborate tetrahydrate;
sodium carbonate peroxyhydrate;
sodium pyrophosphate peroxyhydrate;
urea peroxyhydrate;
sodium peroxide;
and the like including the other alkali metal salts of the above salt
compounds. The more preferred bleaches are the sodium perborate hydrates.
The amount of bleach activator in the bleaching compositions is a function
of the amount of peroxygen bleaching compounds. Preferably there should be
at least a stoichiometric amount of bleach activator. This amount is 1
mole for each mole equivalent of active oxygen in the bleaching compound.
A useful range is about 1-10 and more preferably 1-5 moles of bleach
activator per each mole equivalent of active oxygen in the bleaching
compound.
The bleaching composition can be packaged separately and added as required
to the wash solution. More preferably the bleach composition is
incorporated as part of the laundry detergent package which includes a
surfactant. The surfactant can be one or more compatible surface active
agents of the anionic, nonionic, zwitterionic, amphoteric or cationic
types. Useful anionic surfactants include fatty acid soaps, alkali or
ammonium salts of alkylbenzenesulfonic acids, alpha-olefin sulfonic acids
and the like.
Nonionic surfactants include condensation products of alkylene oxides with
organic hydrophobic compounds such as alkyl phenols or C.sub.8-22
alcohols.
Zwitterionic surfactants include derivatives of C.sub.8-18 aliphatic
quaternary ammonium, phosphonium and sulfonium compounds. In fact the
bleach activators of this invention also function as surfactants.
Laundry detergents usually include builders to remove certain metals from
the laundry solution. Examples of these builders are sodium
polyphosphates, sodium salts of ethylenediamine tetraacetic acid, sodium
salts of nitrilotriacetic acid, natural and synthetic zeolites and the
like. For environmental reasons the preferred builder is Zeolite A.
Other conventional laundry detergent components include suds boosters, suds
suppressors, soil release agents, soil suspending agents, dyes, fillers,
optical brighteners, germicides, perfumes, antioxidants, enzymes,
buffering agents and the like.
A typical laundry detergent of this invention will contain about 1-30,
preferably 5-15 weight percent surfactant, 5-35 weight percent Zeolite A
builder, 1-20 weight percent peroxygen bleaching agent, at least a
stoichiometric amount of bleach activator, fillers, and the like.
Tests were conducted which demonstrated the bleach activator properties of
the invention. The test was adapted from A. H. Gilbert "Effective
Bleaching with Sodium Perborate", Detergent Age, July, 1967, page 30. The
test is based on the rate that a bleach solution converts iodide to iodine
which is measured by titration with aqueous sodium thiosulfate to a
colorless end point.
First a stock surfactant solution was prepared by placing 16.0 grams of
sodium tripolyphosphate and 1.0 grams of sodium lauryl sulfate in a flask
and diluting this with water to 1 liter. A 100 ml portion of the stock
solution was then placed in a 250 ml flask and held at test temperature in
a water bath. Then 0.18 grams of sodium perborate tetrahydrate (10.4
weight percent available oxygen, 1.17 milimoles available oxygen) was
placed in the flask and at the same time the bleach activator in an amount
equal to the moles of available oxygen was added. The time was recorded as
"zero time". After a pre-set time, the test solution was quenched by
adding 15 ml of glacial acetic acid and crushed ice. The quenched test
solution was treated with several crystals of potassium iodide and then
titrated with 0.1 molar aqueous sodium thiosulfate to a colorless end
point. From this the amount of oxygen available at the quenched time could
be calculated. The amount of oxygen made available by bleach activators of
this invention at various quench times and temperatures is given in the
following tables. Without any activator the available oxygen would be nil
even at 120.degree. F.
TABLE 1
______________________________________
Test at 90.degree. F.
Available Oxygen (m moles)
At Quench Time (min.)
Activator
5 7 10 15
______________________________________
A. 3.3 .times. 10.sup.-5
3.4 .times. 10.sup.-5
3.4 .times. 10.sup.-5
2.1 .times. 10.sup.-5
B. 9 .times. 10.sup.-5
1.3 .times. 10.sup.-4
1.0 .times. 10.sup.-5
6.8 .times. 10.sup.-5 *
______________________________________
*at 12 minutes
__________________________________________________________________________
Test at 120.degree. F.
Available Oxygen (m moles)
At Quench Time (min.)
Activator
2 3 5 10 15
__________________________________________________________________________
A. 2.9 .times. 10.sup.-5
4.8 .times. 10.sup.-5
2.9 .times. 10.sup.-5
2.3 .times. 10.sup.-5
1.1 .times. 10.sup.-5
B. 1.8 .times. 10.sup.-4
1.1 .times. 10.sup.-4 *
C. 1.0 .times. 10.sup.-4
1.6 .times. 10.sup.-5
5.6 .times. 10.sup.-6
__________________________________________________________________________
*at 7 minutes
Test Bleach Activators
A. didecylmethyl 2acetyloxyethylammonium bromide
B. hexadecyldimethyl 2acetyloxyethylammonium bromide
C. octyldimethyl 2acetyloxyethylammonium bromide
The tests show that the bleach activators of the invention are effective at
temperatures as low as 90.degree. F. In addition the present activators
have surfactant, germicidal and fungicidal properties.
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